CN102066460B - 用于制备多元醇的方法 - Google Patents
用于制备多元醇的方法 Download PDFInfo
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- CN102066460B CN102066460B CN2009801226394A CN200980122639A CN102066460B CN 102066460 B CN102066460 B CN 102066460B CN 2009801226394 A CN2009801226394 A CN 2009801226394A CN 200980122639 A CN200980122639 A CN 200980122639A CN 102066460 B CN102066460 B CN 102066460B
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- China
- Prior art keywords
- polyvalent alcohol
- oxyalkylene
- mol
- catalyzer
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract
本发明的主题是可用简单方法获得的多元醇。除非另外明确指出，所公开的多元醇意欲被解释为聚醚多元醇和聚醚酯多元醇。本发明的主题还是所述的简单方法本身，以及按照本发明的多元醇用于制备聚氨酯材料的用途。
Description
技术领域
本发明的主题是可用简单方法获得的多元醇。本发明的主题还是该方法本身，以及本发明多元醇用于制备聚氨酯材料的应用。
背景技术
适合聚氨酯材料如软或硬泡沫塑料或诸如弹性体之类实心材料的生产用多元醇，通常可通过适当氧化烯在多官能启动化合物，即包含多个泽尔维季诺夫活泼氢原子的启动化合物，上的聚合获得。早已公知，有各种各样实施此类聚合反应的方法，这些方法中有些则互为补充：
一方面，氧化烯在具有泽尔维季诺夫活泼氢原子的启动化合物上的碱催化加成反应在大规模生产上很重要；另一方面，为实施这一反应，双金属氰化物化合物(“DMC 催化剂”)的应用正变得日益重要。采用高活性DMC催化剂，例如在US-A 5 470 813, EP-A 700
949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310和WO 00/47649中描述的那样，有可能制备催化剂浓度非常低(25 ppm 或更少)的聚醚多元醇，以致不再需要将催化剂从最终产物中分离出去。然而，此种催化剂不适合短链多元醇或基于含氨基基团启动化合物的多元醇的制备。早已公知的碱性催化剂，例如，基于碱金属氢氧化物的那些，虽能实现短链多元醇和/或基于氨基基团启动化合物的多元醇的顺利制备，但该催化剂通常必须借助单独后加工步骤从碱性粗聚合物中移出。特别是在含氨基基团多元醇的制备的情况下，常常获得黄色至泛黄-褐色产物；带色的原材料对于某些应用场合，例如，在清漆和涂料的情况下，是不期望的。氧化烯在适当启动化合物上的(路易斯)酸-催化加成则重要性不大。
氧化烯诸如例如环氧乙烷或环氧丙烷在具有泽尔维季诺夫活泼氢原子的启动化合物上的碱催化加成反应，如上已经所述的，是在碱金属氢氧化物的存在下实施的，但碱金属氢化物、碱金属羧酸盐、碱土金属氢氧化物或胺诸如例如N,N-二甲基苄基胺或咪唑或咪唑衍生物，也可使用。在具有键合在氮原子上的泽尔维季诺夫活泼氢原子的含氨基基团启动化合物的情况下，在没有催化作用的情况下，每摩尔泽尔维季诺夫活泼氢原子最高可加成1 mol氧化烯；如果超过这一比值，则通常必须加入上面所列碱性催化剂之一。当加入氧化烯时，必须钝化聚醚链上的聚合活性中心。为此，可采用各种各样的程序。例如，可利用稀无机酸如硫酸或磷酸来实施中和。硫酸的第二解离阶段的强度足以使通过活性烃氧基基团水解生成的碱金属氢氧化物发生质子化，因此，每mol所使用的硫酸，可中和2 mol烃氧基基团。另一方面，磷酸则必须使用相对于要中和的烃氧基基团数量而言“等摩尔”的数量。中和和/或通过蒸馏除水期间生成的盐一般必须借助过滤方法分离。蒸馏-和过滤过程费时且耗能，另外在许多情况下也不容易很好地重复。为此已研发出多种无需过滤步骤，和在许多情况下也无需蒸馏步骤，就能实施的方法。用羟基羧酸（carbonsäuren）诸如例如乳酸进行的中和描述在WO 98/20061和US-A 2004167316中，用以对生产硬泡沫塑料用短链多元醇进行后处理；这些方法被广泛采用并且是相当成熟的方法。US-A 4521548描述如何按照类似方式通过与甲酸起反应使聚合活性中心钝化。用羟基羧酸或甲酸中和后生成的金属羧酸盐在聚醚多元醇中溶解从而产出澄清溶液。然而，此类方法的缺点是留在产物中的盐的催化活性，这对于许多聚氨酯用途来说是不期望的。因此在WO 04/076529中，聚合反应采用10-1000 ppm KOH的低催化剂浓度实施，以便使中和后留在多元醇中的催化活性羟基羧酸盐同样也以低浓度存在，相应地对后续反应的破坏作用也较小。在JP-A 10-30023和US-A 4110268中，采用芳族磺酸或有机磺酸中和：这些酸生成同样可溶于聚醚多元醇，但碱性较小并以低催化活性为特征的盐。这里的一个重要缺点是磺酸的高成本。借助酸性阳离子交换剂的后处理，正如在DE-A 100 24 313中描述的，要求使用溶剂并采用蒸馏移出它们，相应地也带来高成本。相分离方法仅要求水解步骤，不需要中和步骤，并例如描述在WO 01/14456, JP-A
6-157743, WO 96/20972和US-A 3823145中。聚醚多元醇与碱性水相之间的相分离因凝聚池或离心作用的采用得到促进；这里，通常也需要加入溶剂以增加聚醚相与水相之间的密度差。此类方法不适合所有类型的聚醚多元醇；特别是，它们在短链聚醚多元醇或具有高环氧乙烷含量的聚醚多元醇的情况下不成功。溶剂的使用耗费成本，而离心则要求在维修方面的高花费。
在胺催化的氧化烯加成反应的情况下，进一步的后加工可用略去，只要多元醇中胺的存在不干扰聚氨酯材料的生产。利用胺催化只能获得当量比较低的多元醇；关于这方面可参见，例如，Ionescu et al. 在“Advances in Urethane
Science & Technology”, 1998, 14, p. 151-218。
发明内容
因此，本发明的目的是找到一种针对利用碱-或碱土金属氢氧化物、-羧酸盐或-氢化物催化制备的含氨基基团多元醇，包括含环氧乙烷的含氨基基团多元醇，的低成本后加工方法，该方法不具有现有技术方法的缺点。本发明的目的特别是获得一种具有低固有颜色的含氨基基团多元醇。
现已能通过加入0.75～1 mol硫酸每摩尔催化剂实现对粗氧化烯加成产物的碱性、聚合活性中心的中和来达到这一目的。这一程序生产出一种透明产物，它令人吃惊地表现出比采用少于0.75 mol硫酸每摩尔催化剂所中和的产物低的固有颜色。该方法可用于长-和短链聚醚多元醇，就是说，最终产物的羟基值范围从大约20 mg KOH/g 延伸到大约1000 mg KOH/g。聚醚链的结构，就是说多元醇制备中使用的氧化烯（Alkolenoxide）或氧化烯混合物的组成，也允许同样地变化。
详细地说，本发明方法按如下实施：
通常，将启动化合物置于反应器中，而催化剂，就是说，碱金属氢氧化物，碱-、碱土金属氢化物，碱-、碱土金属羧酸盐或碱土金属氢氧化物，则任选地已经在该阶段加入。优选使用碱金属氢氧化物，特别优选氢氧化钾。该催化剂可以水溶液的形式或以固体形式喂入到启动化合物中。以最终产物数量为基准计，催化剂浓度介于0.004～0.1 wt.%, 优选0.01～0.1 wt.%, 特别优选0.025～0.1 wt.%。溶剂水和/或在启动化合物与催化剂的反应中释放出的水可在提高的温度，优选在反应温度，真空下移出，然后再开始计量加入氧化烯，条件是使用的启动化合物具有足够低的蒸汽压。替代地，也可不带催化剂首先加入氧化烯，而碱金属氢氧化物的加入和脱水步骤只有当已达到启动化合物中的足够低蒸汽压时才进行。在低催化剂浓度的情况下，也可能省略脱水。
作为碱性催化剂，也可使用具有烷氧基含量介于0.05～50当量%(“聚合烷氧基化物”)的含泽尔维季诺夫活泼氢原子的启动化合物的预制氧化烯加成产物。该催化剂的烷氧基化物含量应理解为通过碱通过去质子化被除掉的泽尔维季诺夫活泼氢原子的比例，以原来存在于催化剂的氧化烯加成产物中全部泽尔维季诺夫活泼氢原子为基准计。当然，聚合烷氧基化物的用量依赖于对于最终产物用量所要求的催化剂浓度，正如在前面一段中所描述的那样。
键合在N、O或S上的氢，当它按照泽尔维季诺夫发现的方法通过与碘化甲基镁起反应生成甲烷时，即被称作泽尔维季诺夫活泼氢(有时亦仅简称为“活泼氢”)。具有泽尔维季诺夫活泼氢的化合物的典型例子是含有羧基、羟基、氨基、亚氨基或巯基作为官能团的化合物。
被置于反应器中的启动化合物随后与氧化烯在惰性气氛下，在80～180℃, 优选100～170℃的温度起反应，其中氧化烯以传统方式连续喂入到反应器中，以便不致超过所用反应器系统的与安全有关的压力极限。此类反应传统上在10 mbar～10 bar的压力范围实施。如果，如上已经所述，氧化烯，不连带催化剂，首先加入，则氧化烯的计量加入将在适当的点中断，并在经过一段适当后反应时间之后加入催化剂。氧化烯计量加入阶段的终点过后是后反应阶段，期间残留氧化烯将完全起反应。后反应阶段的终点将在从反应容器中不再探测到进一步的压力降低时达到。随后进行针对粗氧化烯加成产物的碱性、聚合活性中心的中和，这是通过加入0.75～1 mol硫酸每摩尔催化剂，优选0.8～1 mol硫酸每摩尔催化剂，特别优选0.9～1 mol硫酸每摩尔催化剂，最特别优选0.95～1 mol硫酸每摩尔催化剂，实施的。中和期间，温度可在宽范围内变化；极限值可由多元醇结构确定。如果水解敏感基团，诸如例如酯基团，存在于产物中，则中和例如可在室温进行。当中和发生后，由通过加入稀酸带入的痕量水可在真空下移出。抗老化剂或抗氧化剂可在中和期间或以后加入到产物中。进一步的后加工步骤，诸如例如产物的过滤，通常是不需要的。然而，也可将产生的盐分离出来，若要求的话。盐的结晶可通过加入水予以加速，水的量介于2 wt%～20 wt%，以碱性聚合产物的质量为基准计，加水可在中和之前或期间实施，随后通过蒸馏将它移出。如此结晶出来的盐可通过过滤分离出去。
合适的含氨基基团启动化合物大多具有1～4的官能度，官能度应理解为每个启动分子中存在的泽尔维季诺夫活泼氢原子的数目。含氨基基团启动化合物优选含有至少一个伯氨基基团(-NH2)和/或仲氨基基团和/或叔氨基基团。其摩尔质量介于17 g/mol 至约1200 g/mol。
含氨基基团启动化合物的例子是氨、乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、二异丙醇胺、乙二胺、六亚甲基二胺、苯胺、甲苯胺的各种异构体、二氨基甲苯的各种异构体、二氨基二苯甲烷的各种异构体以及苯胺与甲醛缩合以生成二氨基二苯甲烷的过程中生成的高级多核产物。当然，也可以使用不同含氨基基团启动化合物的混合物。另外，含氨基基团启动化合物与不含氨基基团的启动化合物的混合物也可使用。含氨基基团启动化合物在该启动化合物的混合物中的含量应至少是20 mol%。不含氨基基团的启动化合物的例子是甲醇、乙醇、1-丙醇、2-丙醇和高级脂族一元醇，特别是脂肪醇，苯酚、烷基取代的苯酚，丙二醇、乙二醇、二甘醇、二丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、己二醇、戊二醇、3-甲基-1,5-戊二醇、1,12-十二烷二醇、甘油、三羟甲基丙烷、季戊四醇、山梨醇、蔗糖、氢醌、邻苯二酚、间苯二酚、双酚F、双酚A、1,3,5-三羟基苯，或甲醛与苯酚的含羟甲基基团的缩合产物。另外，嘧胺或脲以及曼尼希碱都可当作(共)启动化合物使用。
另外，还可在该方法中加入所提到的含氨基基团或无氨基基团启动化合物的预制氧化烯加成产物，就是说，羟基值介于20～1000 mg KOH/g, 优选250～1000 mg KOH/g的聚醚多元醇。除了启动化合物之外，还可能在本发明方法中使用羟基值在6～800 mg KOH/g范围内的聚酯多元醇，旨在制备聚醚酯。适合该目的的聚酯多元醇可由，例如，2～12个碳原子的有机二羧酸与2～12个碳原子，优选2～6个碳原子的多羟基醇，优选二醇，按公知的方法制备。
在当前石油资源短缺以及化石类原料受到基于生态平衡的不利评价的背景下，来自可再生来源原料的应用对于适用于聚氨酯工业的多元醇的制备也变得日益重要。本发明方法通过在氧化烯加入之前或期间向方法中加入10～80 wt%用量的，以最终产物的数量为基准计，诸如例如以下甘油三酯开创了此类多元醇制备的高度经济的可能性：豆油、菜籽油、棕榈仁油、棕榈油、亚麻籽油、向日葵油、青鱼油、沙丁鱼油、Lesquerellaöl和蓖麻油。获得这样一种聚醚酯多元醇：这些油已被完全结合到该多元醇的结构中，以致这些油在最终产物中不再能检测出来，或者仅能检测出非常少的数量。令人惊奇的是，不带羟基基团的油在该方法变体中也能生产出均质最终产物。
所述可作为催化剂使用的聚合烷氧基化物是在单独反应步骤中通过氧化烯在含泽尔维季诺夫活泼氢原子的启动化合物上加成制成的。传统上，在聚合烷氧基化物的制备中，0.1～1 wt%，以要制备的数量为基准计，的碱-或碱土金属氢氧化物，例如，KOH，被用作催化剂，必要的话，反应混合物在真空下脱水，氧化烯加成反应在惰性气氛下在100～170℃一直反应到达到羟基值为150～1200 mg KOH/g，然后，整个反应物料任选地通过进一步加入碱-或碱土金属氢氧化物并随后脱水而调节到0.05～50当量%的上述烷氧基化物含量。如此制备的聚合烷氧基化物可在惰性气氛下单独贮存。然后它们在本发明方法中的使用尤其优选是当使用在碱性条件下对水解敏感的材料时，或者当低分子量启动化合物在长链多元醇的制备中的数量不足以保证反应开始时反应混合物的充分混合时。另外，某些低分子量启动化合物具有生成难溶碱-或碱土金属盐的倾向；在这样的情况下，也推荐首先通过上面描述的方法将启动化合物转变为聚合烷氧基化物。在本发明方法中使用的聚合烷氧基化物的用量通常应如此测定，使其与碱-或碱土金属氢氧化物浓度，以要制备的本发明最终产物的数量为基准计，相对应，介于0.004～0.1 wt.%, 优选0.01～0.1 wt.%, 特别优选0.025～0.1 wt.%。自然，聚合烷氧基化物也可以以混合物的形式使用。
合适的氧化烯例如是，环氧乙烷、环氧丙烷、1,2-环氧丁烷或2,3-环氧丁烷。优选使用环氧丙烷和环氧乙烷。各种不同氧化烯可以混合物形式或呈嵌段形式计量加入。含有环氧乙烷链端嵌段的产物以，例如，给体系带来模塑泡沫塑料用途所需异氰酸酯活性的伯端基浓度的增加来表征。
碱性粗多元醇一般具有20～1000 mg KOH/g的羟基值, 优选 28～700 mg KOH/g的羟基值。
可按照本发明方法获得的多元醇可作为起始组分用于生产实心或发泡聚氨酯材料和聚氨酯弹性体。聚氨酯材料和-弹性体还可包含异氰尿酸酯、脲基甲酸酯和缩二脲结构单元。也可以制备所谓异氰酸酯预聚物，在该制备中，采取大于1的异氰酸酯基团与羟基基团之间的摩尔比值，以便使产物含有游离的异氰酸酯官能度。其直至在1或多个步骤中在制备实际最终产物时才起反应。
为生产这样的材料，本发明多元醇任选地与附加的异氰酸酯活性组分进行混合并与有机多异氰酸酯起反应，任选地在发泡剂的存在下，在催化剂的存在下，任选地在其他添加剂，例如，泡孔稳定剂的存在下。
具体实施方式
实施例
使用的原料:
Irganox
1076:
3-(3,5-二-叔丁基-4-羟基苯基)丙酸十八烷基酯
实施例
1
1046.1 g乙二胺在氮气氛下引入到10 L实验室压热釜中。关闭注入管嘴后，残留氧气通过3次施加3 bar 氮压，随后从超压释放至大气压压力被赶出。在搅拌(450 rpm)下加热至150℃，然后将3711.5 g环氧丙烷在3 h时间内计量加入到压热釜中。随后，让混合物后反应（nachreagieren）1 h，继而冷却至80℃。在加入2.815 g的44.82 wt.% 浓度的KOH水溶液后，在1 h时间内通过以氮气(50 ml/min)汽提在150℃、真空(20 mbar)下移出水。然后，在2.5 h时间内计量加入1244.2 g环氧丙烷。接着，是1.5 h的后反应时间。在真空中加热30 min.并冷却至室温后，从浴中提取2份浴液进行中和试验(实施例 1A和1B)。催化剂浓度(KOH)是210 ppm。
实施例
1A(
对比例
)
将2.028 g 11.82%浓度的硫酸, 对应于 0.50 mol 硫酸每摩尔KOH, 在 80℃加入到 1305.2 g 来自实施例 1的产物中，并在80℃搅拌1 h。加入0.88 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
1B
将4.064 g 11.82%浓度的硫酸, 对应于1.00 mol 硫酸每摩尔KOH, 在 80℃ 加入到 1307.6 g实施例1的产物中,并在80℃搅拌1 h。加入0. 885 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
2
1049 g乙二胺在氮气氛下引入到10 L实验室压热釜中。关闭注入管嘴后，残留氧气通过3次施加3 bar 氮压，随后从超压释放至大气压压力被赶出。在搅拌(450 rpm)下加热至150℃，然后将3735 g环氧丙烷在3 h时间内计量加入到压热釜中。随后，让混合物后反应1 h，继而冷却至80℃。在加入6.922 g 44.82 wt.%浓度的KOH水溶液后，在1 h时间内通过以氮气(50 ml/min)汽提在150℃、真空(20 mbar)下移出水。然后，在1 h时间内计量加入1252.2 g环氧丙烷。接着，是1.5 h的后反应时间。在真空中加热30 min.并冷却至室温后，从浴中提取2份浴液进行中和试验(实施例 1A和1B)。催化剂浓度(KOH)是510 ppm. (实施例 2A, 2B, 2C, 2D和2E)。
实施例
2A(
对比例
)
将4.509 g 11.82%浓度的硫酸, 对应于0.51 mol 硫酸每摩尔KOH, 在 80℃加入到1183.5 g 来自实施例 2的产物中，并在80℃搅拌1 h。加入0.792 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
2B
将8.971 g 11.82%浓度的硫酸, 对应于1.00 mol 硫酸每摩尔KOH, 在 80℃ 加入到1179.3 g实施例2的产物中,并在80℃搅拌1 h。加入0.799 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
2C (
对比例
)
将1.238 g 85%浓度的磷酸, 对应于0.99 mol 磷酸每摩尔KOH, 在 80℃ 加入到1192.8 g实施例2的产物中,并在80℃搅拌1 h。加入0.814 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得浑浊产品。
实施例
2D(
对比例
)
将110 ml 蒸馏水和4.426 g 11.87%浓度的硫酸, 对应于0.50 mol 硫酸每摩尔KOH, 在 80℃ 加入到1189.7 g实施例2的产物中,并在80℃搅拌1 h。加入0.797 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。经配备来自Pall公司的T 750深床过滤器的实验室抽滤器过滤后，获得透明产品。
实施例
2E
将106 ml 蒸馏水和8.819 g 11.87%浓度的硫酸, 对应于0.99 mol 硫酸每摩尔KOH, 在 80℃ 加入到1182.4 g实施例2的产物中,并在80℃搅拌1 h。加入0.790 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。经配备来自Pall公司的T 750深床过滤器的实验室抽滤器过滤后，获得透明产品。
实施例
3
将1025.2 g乙二胺在氮气氛下引入到10 L实验室压热釜中。关闭注入管嘴后，残留氧气通过3次施加3 bar 氮压，随后从超压释放至大气压压力被赶出。在搅拌(450 rpm)下加热至150℃，然后将3725.7 g环氧丙烷在3 h时间内计量加入到压热釜中。随后，让混合物后反应1 h，继而冷却至80℃。在加入13.668 g 44.82 wt.%浓度的KOH水溶液后，在1 h时间内通过以氮气(50 ml/min)汽提在150℃、真空(20 mbar)下移出水。然后，在1 h时间内计量加入1249.1 g环氧丙烷。接着，是1.5 h的后反应时间。随后，碱性粗产物在150℃、真空下再加热30 min。催化剂浓度(KOH)是1020 ppm。
实施例
3A(
对比例
)
将9.969 g 11.87%浓度的硫酸, 对应于0.50 mol 硫酸每摩尔KOH, 在 80℃加入到1327.4 g 来自实施例 3的产物中，并在80℃搅拌1 h。加入0.891 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
3B
将19.532 g 11.87%浓度的硫酸, 对应于1.00 mol 硫酸每摩尔KOH, 在 80℃加入到1299.8 g 来自实施例 3的产物中，并在80℃搅拌1 h。加入0.891 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得透明产品。
实施例
4
756.8 g乙二胺在氮气氛下引入到10 L实验室压热釜中。关闭注入管嘴后，残留氧气通过3次施加3 bar 氮压，随后从超压释放至大气压压力被赶出。在搅拌(450 rpm)下加热至150℃，然后将2769.8 g环氧丙烷在3 h时间内计量加入到压热釜中。随后，让混合物后反应1 h，继而冷却至80℃。在加入6.967 g 44.83 wt.%浓度的KOH水溶液后，在1 h时间内通过以氮气(50 ml/min)汽提在150℃、真空(20 mbar)下移出水。然后，在1 h时间内计量加入2476.4 g环氧丙烷。接着，是2 h的后反应时间。随后，碱性粗产物在150℃、真空下再加热30 min。催化剂浓度(KOH)是520 ppm。
实施例
4A(
对比例
)
将1.4325 g 85%浓度的磷酸, 对应于0.99 mol 磷酸每摩尔KOH, 在 80℃ 加入到1347.8 g实施例4的产物中,并在80℃搅拌1 h。加入0.911 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。获得浑浊产品。
实施例
4B(
对比例
)
将118 ml 蒸馏水和4.934 g 11.87%浓度的硫酸, 对应于0.49 mol 硫酸每摩尔KOH, 在 80℃ 加入到1303.8 g实施例4的产物中,并在80℃搅拌1 h。加入0.881 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。经配备来自Pall公司的T 750深床过滤器的实验室抽滤器过滤后，获得透明产品。
实施例
4C
将118 ml 蒸馏水和9.892 g 11.87%浓度的硫酸, 对应于0.99 mol 硫酸每摩尔KOH, 在 80℃ 加入到1301.6 g实施例4的产物中,并在80℃搅拌1 h。加入0.883 g Irganox
1076后，产物在18 mbar (水力引射真空) 脱水1 h，随后在110℃和1 mbar下脱水3 h。经配备来自Pall公司的T 750深床过滤器的实验室抽滤器过滤后，获得透明产品。
试验结果总括在表1中。
表
1
色值是按照DIN 53995的规定测定的，而羟基值则是按照DIN 53240的规定测定的。
Claims (6)
1.用于制备多元醇的方法，该方法包括氧化烯在基于碱金属氢氧化物，碱金属氢化物、碱土金属氢化物，碱金属羧酸盐、碱土金属羧酸盐或碱土金属氢氧化物的催化剂存在下在含氨基基团启动化合物上的碱催化加成，催化剂的浓度，以最终产物数量为基准计，介于0.004～0.1 wt%，其中多元醇的中和以0.75～1 mol硫酸每mol所使用的催化剂来进行。
2.权利要求1的方法，其中所生成的盐不分离出去。
3.权利要求1的方法，其中2 wt%～20 wt%水，以多元醇为基准，在中和之前和/或期间和/或之后加入，而盐则在水被移出后分离出去。
4.权利要求1至3中任一项的方法，其中10～80 wt%，以最终产物数量为基准计，的甘油三酯在氧化烯加入之前或期间被加入。
5.多元醇，其按照权利要求1至3中任一项的方法获得。
6.按照权利要求5的多元醇用于制备聚氨酯的应用。
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| CN103429638B (zh) * | 2010-12-20 | 2016-06-22 | 拜耳知识产权有限责任公司 | 聚醚多元醇的制备方法 |
| CN102585197A (zh) * | 2011-01-05 | 2012-07-18 | 辽宁科隆精细化工股份有限公司 | 环氧化物加成的方法以及碱金属及其盐用于该方法的用途 |
| MX337785B (es) | 2013-02-22 | 2016-03-18 | Bayer Materialscience Ag | Procedimiento de preparacion de polioles de polieter. |
| SG2014014567A (en) | 2013-02-22 | 2014-09-26 | Bayer Materialscience Ag | Process for preparing polyether polyols |
| US10961346B2 (en) | 2016-05-13 | 2021-03-30 | Covestro Deutschland Ag | Method for the preparation of polyoxyalkylene polyols |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0050181A1 (en) * | 1980-10-20 | 1982-04-28 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for purifying polyether-polyols |
| US6762214B1 (en) * | 2003-03-18 | 2004-07-13 | Bayer Polymers Llc | Process for the production of rigid foams from alkaline polyether polyols |
| CN101033285A (zh) * | 2007-02-14 | 2007-09-12 | 南京红宝丽股份有限公司 | 采用菜籽油制备的软质聚氨酯泡沫塑料 |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823145A (en) | 1968-07-26 | 1974-07-09 | Basf Wyandotte Corp | Removal of impurities from polyols |
| US4110268A (en) | 1976-09-27 | 1978-08-29 | Witco Chemical Corporation | Polyether polyols and polyurethane foams made therefrom |
| US4521548A (en) | 1983-04-12 | 1985-06-04 | The Dow Chemical Company | Preparation of polyether polyols |
| DE3928397A1 (de) * | 1989-08-28 | 1991-03-07 | Henkel Kgaa | Verfahren zur herstellung von salzfreien estern von fettsaeuren mit oligoglycerinen bzw. mit anlagerungsprodukten von ethylenoxid und/oder propylenoxid an oligoglycerine |
| US5220077A (en) * | 1992-08-19 | 1993-06-15 | Vista Chemical Company | Alkoxylation process |
| JP3263450B2 (ja) | 1992-11-27 | 2002-03-04 | 三井化学株式会社 | 粗ポリオキシプロピレンポリオールの精製方法 |
| US5304665A (en) * | 1993-04-05 | 1994-04-19 | Arco Chemical Technology, L.P. | Process for the preparation of highly esterified alkoxylated polyol compositions |
| US5470813A (en) | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
| US5712216A (en) | 1995-05-15 | 1998-01-27 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
| US5482908A (en) | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
| WO1996020972A2 (en) | 1995-01-05 | 1996-07-11 | Bayer Corporation | A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL |
| US5545601A (en) | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
| JP3651994B2 (ja) * | 1996-01-12 | 2005-05-25 | 三井化学株式会社 | ポリオキシアルキレンポリオールおよびその製造方法 |
| US5627120A (en) | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
| JPH1030023A (ja) | 1996-07-16 | 1998-02-03 | Asahi Glass Co Ltd | ポリ（またはモノ）オール組成物およびポリウレタンの製造方法 |
| DE19629525A1 (de) * | 1996-07-22 | 1998-01-29 | Basf Ag | Verwendung von Naphthalinsulfonsäure-Formaldehyd-Kondensationsprodukten als Trocknungshilfsmittel |
| US5714428A (en) | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
| US5786405A (en) | 1996-11-01 | 1998-07-28 | Bayer Corporation | Amine-initiated polyether polyols and a process for their production |
| DE19807991A1 (de) * | 1998-02-26 | 1999-09-02 | Clariant Gmbh | Alkoxylierungskatalysator |
| DE19905611A1 (de) * | 1999-02-11 | 2000-08-17 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
| US6376625B1 (en) | 1999-08-25 | 2002-04-23 | The Dow Chemical Company | Process for purifying polyethers |
| DE10024313A1 (de) * | 2000-05-17 | 2001-11-22 | Basf Ag | Verfahren zur Abtrennung von Alkalimetallionen aus Alkoxylaten |
| US6869543B2 (en) | 2003-02-21 | 2005-03-22 | Bayer Polymers Llc | Amine-initiated polyether polyols and a process for their production |
| JP4290141B2 (ja) * | 2004-07-29 | 2009-07-01 | 三洋化成工業株式会社 | ポリエーテルの精製方法 |
| US20070213554A1 (en) * | 2005-09-01 | 2007-09-13 | Matheson Kenneth L | Process for preparing alkoxylation catalyst and alkoxylation process |
| DE102007038436A1 (de) * | 2007-08-16 | 2009-02-19 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyolen |
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2008
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2009
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- 2009-06-04 CN CN2009801226394A patent/CN102066460B/zh not_active Expired - Fee Related
- 2009-06-04 PT PT09765534T patent/PT2291434E/pt unknown
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- 2009-06-04 KR KR1020107028169A patent/KR20110029125A/ko active IP Right Grant
- 2009-06-04 MX MX2010013859A patent/MX2010013859A/es active IP Right Grant
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- 2009-06-04 BR BRPI0914792A patent/BRPI0914792A2/pt not_active IP Right Cessation
- 2009-06-04 WO PCT/EP2009/003981 patent/WO2009152954A1/de active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0050181A1 (en) * | 1980-10-20 | 1982-04-28 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for purifying polyether-polyols |
| US6762214B1 (en) * | 2003-03-18 | 2004-07-13 | Bayer Polymers Llc | Process for the production of rigid foams from alkaline polyether polyols |
| CN101033285A (zh) * | 2007-02-14 | 2007-09-12 | 南京红宝丽股份有限公司 | 采用菜籽油制备的软质聚氨酯泡沫塑料 |
Also Published As
| Publication number | Publication date |
|---|---|
| US8501904B2 (en) | 2013-08-06 |
| PL2291434T3 (pl) | 2013-01-31 |
| WO2009152954A1 (de) | 2009-12-23 |
| US20110105714A1 (en) | 2011-05-05 |
| EP2291434B1 (de) | 2012-08-08 |
| DE102008028555A1 (de) | 2009-12-17 |
| CA2727743C (en) | 2016-01-19 |
| JP5528437B2 (ja) | 2014-06-25 |
| CA2727743A1 (en) | 2009-12-23 |
| CN102066460A (zh) | 2011-05-18 |
| EP2291434A1 (de) | 2011-03-09 |
| JP2011524448A (ja) | 2011-09-01 |
| KR20110029125A (ko) | 2011-03-22 |
| BRPI0914792A2 (pt) | 2015-10-20 |
| PT2291434E (pt) | 2012-10-23 |
| MX2010013859A (es) | 2011-02-24 |
| ES2391534T3 (es) | 2012-11-27 |
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